US4507459A - Polyurethane compositions having low hysteresis - Google Patents

Polyurethane compositions having low hysteresis Download PDF

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Publication number
US4507459A
US4507459A US06/578,240 US57824084A US4507459A US 4507459 A US4507459 A US 4507459A US 57824084 A US57824084 A US 57824084A US 4507459 A US4507459 A US 4507459A
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United States
Prior art keywords
polyol
diamine
prepolymer
urethane composition
chain extender
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Expired - Fee Related
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US06/578,240
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English (en)
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Andreas R. Schmidt
Herbert F. Strohmayer
Walter Sibral
Barton Milligan
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Lim International SA
Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Assigned to LIM INTERNATIONAL S.A., AIR PRODUCTS AND CHEMICALS, INC. reassignment LIM INTERNATIONAL S.A. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MILLIGAN, BARTON, SCHMIDT, ANDREAS R., STROHMAYER, HERBERT F., SIBRAL, WALTER
Priority to US06/578,240 priority Critical patent/US4507459A/en
Priority to CA000470028A priority patent/CA1236629A/en
Priority to AU37986/85A priority patent/AU3798685A/en
Priority to ZA85736A priority patent/ZA85736B/xx
Priority to ES540005A priority patent/ES8706746A1/es
Priority to HU85465A priority patent/HUT38665A/hu
Priority to JP60021016A priority patent/JPS60181117A/ja
Priority to BR8500570A priority patent/BR8500570A/pt
Priority to EP85101293A priority patent/EP0153628A1/en
Publication of US4507459A publication Critical patent/US4507459A/en
Application granted granted Critical
Priority to CN 85101894 priority patent/CN85101894A/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2350/00—Acoustic or vibration damping material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2380/00—Tyres

Definitions

  • This invention relates to polyurethane molding compositions having low hysteresis. These molding compositions are well suited for high shock and vibration environments.
  • polyurethane elastomer formulations in the manufacture of molded products by a variety of techniques which include injection molding, rotational molding or casting and reaction injection molding (RIM) is widely known.
  • RIM reaction injection molding
  • These formulations for use in various applications are formed by reacting a polyisocyanate with a polyol and, in some cases, then chain extending with a diamine or polyol chain extender to provide rigidity.
  • such formulations will utilize an aromatic diisocyanate, a polyol, and a diamine chain extender.
  • Molded products for use in applications such as motor mounts, shock absorber, and vibration dampeners must have an ability to resist heat build up due to internal frictional causes and they must be impact resistant.
  • Tires either for passenger car service or larger tires as, for example, trucks and farm tractors, have to meet rigid requirements in terms of impact resistance, abrasion resistance and thermal resistance, etc. Tires are also exposed to heavy flexing and internal heat is generated which can cause thermal degradation of the polymer. To withstand this flexing the polymers must have a low hysteresis in order to avoid excessive heat generation. Further because tires are of significant size, they present an additional problem with respect to their manufacture. The processing techniques have to be closely mentioned so that gelation does not occur prior to filling the mold.
  • U.S. Pat. No. 2,173,884 shows the manufacture of a tire composition having a tread section of polyester-diisocyanate elastomer bonded with an adhesive formulation of polyalkylene ether glycol diisocyanate elastomer to a rubber tire stock.
  • the polyester diisocyanate elastomer was formed by reacting adipic acid with ethylene and propylene glycol with 4,4'-methylene diphenyl diisocyanate.
  • U.S. Pat. No. 4,044,811 shows the manufacture of a laminated tire which utilizes a polyurethane formed from a prepolymer of toluene diisocyanate and a polyalkylene glycol such as poly(tetramethylene ether glycol) and a diamine chain extender such as ethylene diamine, methylene-bis-(2-chloroaniline) (MOCA) and the like.
  • a polyurethane formed from a prepolymer of toluene diisocyanate and a polyalkylene glycol such as poly(tetramethylene ether glycol) and a diamine chain extender such as ethylene diamine, methylene-bis-(2-chloroaniline) (MOCA) and the like.
  • a polyurethane formed from a prepolymer of toluene diisocyanate and a polyalkylene glycol such as poly(tetramethylene ether glycol) and a diamine chain extend
  • U.S. Pat. No. 4,090,547 shows the manufacture of a urethane tire wherein the urethane is formed by reacting a prepolymer of poly(tetramethylene ether glycol) and toluene diisocyanate having an isocyanate content of about 4% with metaphenylene diamine as a chain extender. Similar formulations utilize MOCA as the chain extender.
  • U.S. Pat. No. 3,563,906 discloses formaldehyde condensed amine curing agents for liquid isocyanato-terminated polyurethanes.
  • Representative amine curing agents include hindered or negatively substituted aromatic diamines such as methylene bis-chloroaniline, and dichlorobenzidine.
  • the formaldehyde condensed amines have moderate reactivity and a limited tendency to crystallize under operating conditions.
  • U.S. Pat. No. 3,194,793 discloses polyurethane mixtures cured with aromatic primary and secondary amines.
  • Representative amines include 4,4'-methylene-bis(2-chloroaniline) (MOCA), diphenyl propylenediamine, diamino diphenyl ether, naphthalene diamine, toluene diamine, various halogenated and alkoxylated benzidines, e.g. dimethoxy benzidine and dichlorodimethyl benzidene.
  • U.S. Pat. No. 4,017,464 discloses polyurethane compositions formed by reacting toluene diisocyanate with polytetramethylene ether diol and then cross-linking with a diamino diphenyl disulfide curing agent. Such compositions are alleged to be well suited for tire manufacture.
  • U.S. Pat. No. 4,002,584 discloses urethane elastomers formed by reacting a long chain polyol with an organic diisocyanate and a halogenated aromatic diamine such as methylene-bis-dichloroaniline, dichlorodibromodiaminodiphenyl methane, tetrabromobenzidine and other halogenated aromatic diamines.
  • a halogenated aromatic diamine such as methylene-bis-dichloroaniline, dichlorodibromodiaminodiphenyl methane, tetrabromobenzidine and other halogenated aromatic diamines.
  • U.S. Pat. No. 3,846,351 discloses a method for preparing flexible polyurethane foams by reacting a polyether polyol with an organic diisocyanate and cross-linking with a dialkyl paraphenylene diamine.
  • chain extenders include diisopropylphenylenediamine, di-sec butyl-paraphenylene diamine.
  • U.S. Pat. No. 4,254,272 discloses polyurethanes formed by reacting an organic diisocyanate with a polyol and then curing with a substituted aromatic diamine consisting of diamino-tert-alkyl benzoates and diamino-tert-alkyl benzonitriles.
  • a substituted aromatic diamine consisting of diamino-tert-alkyl benzoates and diamino-tert-alkyl benzonitriles.
  • Specific examples of the diamines include methyl diamino-tert-butyl benzoate; octadecyl diamino-tert-butyl benzoate and comparable alkyl benzonitriles.
  • U.S. Pat. No. 3,736,295 discloses the preparation of polyurethane elastomers by reacting an organic diisocyanate with an organic polyol utilizing an aromatic diamine containing ether groups and chlorine atoms in the ortho position as a chain extender.
  • U.S. Pat. No. 3,752,790 discloses various amine curing agents for liquid polyurethanes having free isocyanate groups. Examples include dichlorotoluene diamine and chlorotoluene diamine as the amine curing agents. The chlorinated toluene diamines are alleged to improve hardness and modulus of the urethane composition.
  • U.S. Pat. Nos. 4,048,105; 4,218,543 disclose molding urethane formulations by the technique of reaction injection molding (RIM).
  • the systems utilize a formulation consisting of a quasi-prepolymer consisting of the reaction product of a low molecular weight diol or triol and an organic isocyanate e.g. methylene bis(4-phenyl isocyanate) with a polyol blend consisting of polyol, amine chain extender and catalyst.
  • the amine chain extenders include the unhindered aromatic polyamine, such as methylene dianiline (MDA).
  • the '543 patent uses an alkylated diamine, such as diethyltoluene diamine as a chain extender in a RIM process. These alkylated aromatic diamines result in extending gelation time as compared to the unhindered aromatic diamines.
  • alkylated diamines result in extending gelation time as compared to the unhindered aromatic diamines.
  • isocyanates and amine chain extenders were selected on the basis of reactivity and performance. Reactivity was altered by using an inactive isocyanate with an active diamine or vice versa. Performance was generally good because of the inherent abrasion resistance and toughness of the urethane polymer.
  • urethane polymers have good physical properties and are suited for application in tires, they have enjoyed little commercial success. They simply have not competed with rubber for tires in terms of high speed performance and cost.
  • This invention relates to an improved polyurethane composition formed by reacting (1) a prepolymer formed by reacting (a) an aromatic polyisocyanate represented by the formula: ##STR1## where R 1 , R 2 , R 3 and R 4 are hydrogen, alkyl having 1-4 carbon atoms, nitrile, halogen, CO 2 R 5 , CONR 6 R 7 where R 5 is an alkyl group of 1-6 carbon atoms, and R 6 and R 7 are hydrogen or an alkyl of 1-6 carbon atoms.
  • said polyol being present in an amount to provide from 0.5 to 5 equivalent amine per equivalent polyol by weight of said chain extender mix and then curing the resulting reaction product.
  • the resulting polyurethane molding compositions have a low hysteresis such that when loaded and compressed (flexed) in rapid manner there is low heat buildup;
  • the polyurethane has good tear propagation resistance
  • FIG. 1A represents the formula for a prepolymer of toluene diisocyanate chain extended with toluene diamine.
  • the view shows that section where the toluene diisocyanate is combined with the toluene diamine and excludes the polyol portion.
  • FIG. 1B represents the formula for a prepolymer toluene diisocyanate chain extended with methylene-bis(2-chloroaniline). The view shows that section where the toluene diisocyanate is combined with the diamine and excludes the polyol.
  • a prepolymer is formed by reacting an aromatic isocyanate of the formula: ##STR3## where R 1 , R 2 , R 3 and R 4 are hydrogen, alkyl having 1-4 carbon atoms, nitrile, halogen, CO 2 R 5 , CONR 6 R 7 where R 5 is an alkyl group of 1-6 carbon atoms, and R 6 and R 7 are hydrogen or an alkyl of 1-6 carbon atoms with a long-chain polyol.
  • the isocyanate as shown can be substituted with a variety of groups without substantially interfering with the hysteresis properties of the polymer. In some cases where a plurality of large alkyl groups is present on the molecule there may be some steric hindrance as compared to a short chain, mono alkyl substituted molecule such as toluene diisocyanate.
  • Specific isocyanates suited for practicing the invention include toluene diisocyanate, phenyl diisocyanate, xylyl diisocyanate, diethyl toluene diisocyanate, and chlorotoluene diisocyanate.
  • the polyol used in forming the prepolymer is either a polyalkylene ether, polylactone or polyester polyol particularly those conventionally used in the production of elastomeric polyurethanes.
  • These polyol systems include organic compounds which contain at least two hydroxyl groups and have a molecular weight from about 500 to 5000 and preferably a molecular weight from about 1,000 to about 3,000.
  • Polyester polyols which are linear or slightly branched can be used and are obtained by the reaction of carboxylic acids and mono or polyhydric alcohols which include amino alcohols and diamino alcohols.
  • polyester polyols examples include oxalic acid, malonic acid, succinic acid, glutaric acid, subaric acid, azelaic acid, maleic acid, fumaric acid and the like as well as hydroxy carboxylic acids.
  • Polyols used in the preparation of the polyester polyols include ethylene glycol, propylene glycol, butylene glycol, pentane diol, hexane diol and heptane diol.
  • polys suited for preparing the polyisocyanate prepolymers include polyether polyols and are derived by condensing an alkylene oxide with an initiator.
  • Initiators generally are difunctional compounds and include glycols such as ethylene glycol, propylene glycol, hexane diol, and the like. Triol functionality can also be used and blended with difunctionality e.g. up to 10% by weight.
  • Preferred polyols are the polyether polyols such as poly(tetramethyleneglycol) and polycaprolactone.
  • the isocyanate and polyol can be reacted together, in conventional manner, to form a prepolymer.
  • the proportion of each reactant is controlled so that there is a free isocyanate content of about 2-12% by weight.
  • the prepolymer may be too reactive with the chain extender mix to achieve proper molding.
  • the molding operation may be excessive in terms of time. Normally, for desirable molding operations, the free isocyanate content is from 3-9% by weight.
  • the chain extender mix used for the polyurethane molding composition consists of an aromatic diamine of the formula: ##STR4## and a polyalkylene ether, polylactone or polyester diol.
  • the polyalkylene ether or polyester diol suitably is the same as that used in manufacturing the prepolymer, but can be any of the polyalkylene ether or polyester diols commonly used. It is incorporated into the chain extender mix in a proportion to provide from about 0.5-5 equivalent amine per equivalent polyol, preferrably 1-3 equivalents amine per equivalent polyol.
  • small amounts of short chain (C 2-14 ) diol or triol chain extender can be included in the chain extender mix such as, for example, up to 10% of the hydroxy functionality.
  • Ethylene glycol, butylene glycol, glycerol or higher polyol, e.g. penterythritol, can be used.
  • a triol or higher polyol e.g. penterythritol
  • the polyurethane molding composition formed by reacting the prepolymer and chain extender mix in the manner described above to produce a product having a low hysteresis is the result of a combination of factors.
  • One factor is that the aromatic diisocyanate and the aromatic diamine chain extender has substantial symmetry between the molecules of the prepolymer and of the chain extender. When the polymer is stretched or flexed, as the case may be, the molecules separate, and upon relaxation, they rejoin through hydrogen bonding at a common angle. Minimum energy is required to break these bonds, and therefore, there is little heat build up in the polymer.
  • joinder cannot occur in the original fashion, or at least joinder in the original fashion is unlikely. As a result the breaking of the rejoined bonds requires more energy and there is increased energy buildup.
  • Another factor in the generation of the polyurethane molding composition is the use of a long chain diluent polyol chain extender with the diamine to permit dispersion of the aromatic diamine into the prepolymer mix prior to reaction.
  • the rate of reaction between the terminal hydroxyl groups of the polyol vis-a-vis the amino groups is perhaps an order of magnitude slower.
  • a series of hard segments are formed by the reaction of the isocyanate with the diamine at uniform locations.
  • a series of soft segments are formed by the reaction of the polyol with the excess diisocyanate. This technique permits the formation of a polymer with soft segments interposed between uniform hard segments.
  • the ratio of free isocyanate content in the prepolymer to amines in the chain extender mix is also related to hysteresis.
  • concentration of NCO typically at the higher end of the range, one uses a lower proportion of amine to polyol in the chain extender mix.
  • NCO content is low, higher levels of amine to polyol can be used.
  • the level of isocyanate content is from 8-12% weight one may utilize amine to hydroxyl levels from 0.5 to 1 equivalent amine per equivalent polyol.
  • At levels from 2-6% NCO one may tolerate levels of 2-5 equivalents amine/equivalent polyol.
  • By varying the ratio of amine to NCO one alters the frequency of hard segments to soft segments and thereby influences the degree of hysteresis.
  • Trifunctional polyols or trifunctional amines when used in formulating the polyurethane molding composition provide too much rigidity through a three dimensional network and do not permit sustained flexing. Accordingly, a difunctional polyol or a difunctional amine is required as a major portion of the polyol in the prepolymer and chain extenders, e.g. 90% or greater equivalent functionality to establish a two-dimensional polymer network.
  • a polyalkylene ether isocyanate prepolymer comprising about 5.17% free NCO groups was prepared in conventional manner from about 1000 g of a linear alkylene polyol i.e. poly(tetramethylene glycol) having a molecular weight of about 2000 and a hydroxyl number of 56, and about 217.7 g of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate in an isomer ratio of about 80:20 by first mixing the components and then heating for about 1 hour at a temperature of 80° C. (Any ratio of 2-4 to 2-6 isomer can be used.)
  • a chain extender mix was prepared by mixing 1,000 g parts of poly(tetramethylene glydol) having a moleculAr weight of 2,000 and a hydroxyl number of 56 with 122 g of toluene diamine, the toluene diamine being the 2:4 and 2:6 isomer and present in a ratio of 80:20.
  • poly(tetramethylene glydol) having a moleculAr weight of 2,000 and a hydroxyl number of 56
  • toluene diamine being the 2:4 and 2:6 isomer and present in a ratio of 80:20.
  • there was included 350 g dioctyl phthalate and 10 g of Metasol catalyst was included.
  • a polyurethane elastomer molding formulation was then formed from the prepolymer and chain extender mix in conventional manner by mixing 60 parts by weight of the chain extender mix with 100 parts by weight of the prepolymer and then curing at a temperature of 100° C.
  • a series of polyurethane molding formulations were prepared in similar manner to the polyurethane molding formulation in Example 1 except that various aromatic diisocyanates, polyols and aromatic diamines were used to prepare the prepolymer and chain extender mix as well as being added in various amounts.
  • the molding formulations are shown in Table 1.
  • Example 1 The polyurethane molding formulations set forth in Example 1 and in Table 1 were evaluated with respect to hysteresis by the use of a modified Goodrich flexometer operated at 25°-30° C.
  • This flexometer is designed to simulate the load experienced by a tire, i.e., the flexing caused by compression and relaxation, of the test sample.
  • a 5-10 gram sample having a cylindrical shape is placed under a fixed load between a plate and plunger. The plunger is moved inwardly and then outwardly to the original loading position at a rate simulating the speed encountered by a tire until the sample fails.
  • the temperature at the center of the polymer cylinder is measured and the failure time recorded.
  • Table 2 provides the end temperature and failure time as well as other various physical properties of the urethane molding formulations of Example 1 and Runs 2 through 15.
  • Run 6 also shows that good polymers can be produced with substituted or slightly hindered aromatic diamine chain extenders such as DETDA, chloro TDA and a carboxylated TDA. Although these particular chain extenders alter the rate in which the polyurethane molding formulation cures, they do not significantly increase the hysteresis of the molding composition to a level comparable to MOCA (Run 5). Run 9 also shows the adverse effect in terms of increased hysteresis when using an aromatic diamine with an aromatic diisocyanate where the symmetry of the chain extender molecule does not match the symmetry of the diisocyanate.
  • substituted or slightly hindered aromatic diamine chain extenders such as DETDA, chloro TDA and a carboxylated TDA.
  • the polyurethane compositions of this invention by virtue of their low hysteresis, have application in the manufacture of tires suited for high speed and for molded products exposed to high shock and vibration environments.
  • Reinforced urethane tires for passenger cars were manufactured using equipment similar to that described in U.S. Pat. No. 4,043,725
  • the tires were loaded at 150% or 615 Kp and initially rotated at a rate to provide a circumferential speed of 75 Km/hr. In another test they were loaded to 410 Kp and rotated for 1 hour at a speed of 180 Km/hr., then 10 minutes at 190 Km/hr. and then at 200 Km/hr. until failure.
  • Tires were prepared from a prepolymer of toluene diisocyanate and poly(tetramethylene ether glycol) (PTMG).
  • a chain extender mix of MOCA and PTMG was used and in another case a chain extender mix of toluene diamine and PTMG was used.
  • the formulations using MOCA as the chain extender were similar to Run 5 of Example 2, and the one using TDA were similar to Example 1.
  • the MOCA chain extended formulations failed much quicker than the tires formulated with toluene diamine chain extenders. In some cases, the tires formulated with the MOCA extended urethane did not even complete the initial test phases. The tires failed due to excessive heat buildup.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
US06/578,240 1984-02-08 1984-02-08 Polyurethane compositions having low hysteresis Expired - Fee Related US4507459A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US06/578,240 US4507459A (en) 1984-02-08 1984-02-08 Polyurethane compositions having low hysteresis
CA000470028A CA1236629A (en) 1984-02-08 1984-12-13 Polyurethane compositions having low hysteresis
AU37986/85A AU3798685A (en) 1984-02-08 1985-01-23 Polyurethanes having low hysteresis
ZA85736A ZA85736B (en) 1984-02-08 1985-01-30 Process for producing polyurethane compositions having low hysteresis
ES540005A ES8706746A1 (es) 1984-02-08 1985-01-31 Procedimiento de producir composiciones de uretano
JP60021016A JPS60181117A (ja) 1984-02-08 1985-02-07 低いヒステリシスを有するポリウレタン組成物の製造方法
HU85465A HUT38665A (en) 1984-02-08 1985-02-07 Process for production of polyurethin forming masses with low hysterisis
BR8500570A BR8500570A (pt) 1984-02-08 1985-02-07 Processo para a producao de composicoes de poliuretano tendo baixa histerese
EP85101293A EP0153628A1 (en) 1984-02-08 1985-02-07 Process for producing polyurethane compositions having low hysteresis
CN 85101894 CN85101894A (zh) 1984-02-08 1985-04-01 低滞后聚氨酯胶料的制备方法

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US06/578,240 US4507459A (en) 1984-02-08 1984-02-08 Polyurethane compositions having low hysteresis

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US (1) US4507459A (ja)
EP (1) EP0153628A1 (ja)
JP (1) JPS60181117A (ja)
AU (1) AU3798685A (ja)
BR (1) BR8500570A (ja)
CA (1) CA1236629A (ja)
ES (1) ES8706746A1 (ja)
HU (1) HUT38665A (ja)
ZA (1) ZA85736B (ja)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786703A (en) * 1987-04-15 1988-11-22 Air Products And Chemicals, Inc. Process for the preparation of polyisocyanate prepolymers and polyurethanes having high temperature performance and low hysteresis
US5112933A (en) * 1991-04-16 1992-05-12 Otis Elevator Company Ether-based polyurethane elevator sheave liner-polyurethane-urea made from polyether urethane prepolymer chain extended with polyester/diamine blend
US5128433A (en) * 1991-06-04 1992-07-07 Polytek Development Corp. Thixotropic polymer compositions and process for use thereof
US20030212236A1 (en) * 2001-05-01 2003-11-13 Luigi Pellacani Process for producing polyurethane elastomer
US20040154718A1 (en) * 2003-02-06 2004-08-12 Doesburg Van I. Polyurethane filled tire and method of making same
US6964626B1 (en) * 1994-07-14 2005-11-15 The Gates Corporation High temperature polyurethane/urea elastomers
US20070148471A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same
US20070149748A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070149747A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070149749A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US20070155935A1 (en) * 2004-09-01 2007-07-05 Rukavina Thomas G Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070155936A1 (en) * 2004-09-01 2007-07-05 Rukavina Thomas G Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070155942A1 (en) * 2004-09-01 2007-07-05 Rukavina Thomas G Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070155895A1 (en) * 2004-09-01 2007-07-05 Rukavina Thomas G Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070167600A1 (en) * 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US20070173582A1 (en) * 2004-09-01 2007-07-26 Rukavina Thomas G Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom
US20070173627A1 (en) * 2004-09-01 2007-07-26 Rukavina Thomas G Poly(ureaurethanes)s, articles and coatings prepared therefrom and methods of making the same
US20070248827A1 (en) * 2004-09-01 2007-10-25 Rukavina Thomas G Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same
US20070251421A1 (en) * 2004-09-01 2007-11-01 Rukavina Thomas G Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same
US20070256597A1 (en) * 2004-09-01 2007-11-08 Rukavina Thomas G Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
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CA1236629A (en) 1988-05-10
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BR8500570A (pt) 1985-09-24
HUT38665A (en) 1986-06-30
EP0153628A1 (en) 1985-09-04
ES540005A0 (es) 1987-07-01
AU3798685A (en) 1985-08-15
ES8706746A1 (es) 1987-07-01
JPS6251967B2 (ja) 1987-11-02

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